Treating oils to produce antiknock gasolines or aromatic type liquids



' J. S. WALTON TREATING OILS TO PRODUCE ANTI-KNOCK GASOLINES 0R AROMATICTYPE LIQUIDS April 4, 1944.

Filed June 29 1940 CYCL owe .szrann 7'02 INJECTOR 5 TEAM INL T CATA I.YST Hawwen JA'PARA TOR ooezy o Patented Apr. 4, 1944 UNITED STATESPATENT OFFICE TREATING OILS T PRODUCE AN'I'IKNOOK GASOLINES 0RAROMA'I'IC TYPE LIQUIDS Jesse S. Walton, Westfield, N. J., assignmtoStandard Oil Development Company, a corporation of Delaware ApplicationJune 29, 1940, Serial No. 343,130 4 Claims. (01. 260-468) ilns, andthereafter to dehydrogenate the cyclooleflns and cyclo-paraffins to formaromatic hydrocarbons. I a

It is a specific object of this invention to crack parafiinichydrocarbons boiling within the kerosene and gas oil range by firstvaporizing the 011, preferably in the presence of 12% water or steamwhere a catalyst is employed, and then subjecting the vapors to crackingconditions to form olefins and parafllns having from 6-8 carbon atoms,then treating the olefins and parafilns under such conditions as to formring compounds and finally dehydrogenating said ring compounds to formaromatics.

Stated otherwise, it is an object of this invention to form fromparaflinic hydrocarbons, arematic hydrocarbons which may be blended withgasoline or motor fuel of relatively low octane number to increasematerially, the octane rating of the motor fuel.

Other and further objects will appear from the r ensuing description.

The single figure of the drawing represents dialine 6. The vapors, onthe other hand, are withdrawn through line 10 and admixed in an injectorl2 with a powdered catalyst, comprising clay or elements of the thirdand sixth group of the periodic system, including aluminum, chromium,and molybdenum or their oxides, or mixtures of these elements ortheiroxides, withdrawn from some source It and dischargedinto thinjector unvaporized product may be withdrawn through I2 through line H.The amount of catalyst admixed with the vapors may vary within ratherwide limits. Good results are obtained by mixing from 2-5 lbs. ofcatalyst per cubic foot of oil vapors measured under the conditions oftemperature and pressure prevailing in the injector It. The suspensionis withdrawn from the injector I2 through line l8 and then passedthrough a reaction zone which may be inthe form of a tank, butpreferably is in the form of a coil 2!! dis posed in the furnace setting2| where more heat may be added to the suspension if desired. The

temperature prevailing in coil 28 should preferably be'within the rangeof from 800 F. to 975 F. andbest results are obtained by maintaining apressure of about 40 lbs. per square inch gauge in this coil. Thehydrocarbons undergo cracking in the coil to form substantiallyequalamounts of oleflnic and parafiinic hydrocarbons and under bestconditions contain a large preponderance of hydrocarbons having from 6-8carbon atoms.

From coil 20 the total product is withdrawn and passed into a third coil25 disposed in a furnace setting 26 where the temperature of the vaporsis increased to a temperature within the range of from 900 F. to 1050F., the pressure conditions being about the same as in coil 20. In thisfurnace the principal reaction is one in which the olefins formed incoil 20 are converted into cyclooleflns or cyclo-parafllns, and theparaffins formed in coil 20 alon with unreacted feed stock are furtherconverted into olefins, cyclo-olefins or cyclo-paraflins. From coil 25,the total product is withdrawn through line 28 and discharged into afourth coil 29 disposed in a furnace setting 30, where the hydrocarbonsare subjected to drawn through line 3| and discharged into'cycloneseparator '32 where'the catalyst is removed from the vapors and passedby gravity into a baflle tower 35 having inclined baflies 36, as

' shown. Steam or some other gas, such as CO2,

nitrogen, flue gas, and the like, heated to approximately 825 F., moreor less, may be introduced into the bottom of the tower through line 31and permitted to flow upwardly against the downcoming catalyst to removethe volatile constituents.- The catalyst is then withdrawn from thebottom of the tower and may be delivered to a regeneration system (notshown) for revivification, according to known methods, for reuse in theprocess.

Meanwhile, the vapors are withdrawn over head through line ll and maythen be passed to a fractionating tower to recover desired products.

namely, aromatic hydrocarbons.

It will be understood, of course, that instead=of using a powderedcatalyst type of operation hereinbefore described, good results areobtained by using beds of stationary catalyst. that is to say, coils 20,25 and 29 may be substituted by cylindrical chambers containingcontinuous beds or separated bodies of catalyst in granular or lump formsupported on perforated trays. The vapors to be treated would .be causedto flow through the bed or beds of catalyst.

To recapitulate, the present invention relates to improvements in theproduction of hydrocarbons having relatively high octane ratings andwhich are particularly suitable for blending with motor fuels ofrelatively low octane value to produce a fuel of satisfactoryperformance. The particular advantages of this invention are believed tolie in the capability of controllin closely, the type of reactions whichoccur in each of the various steps and by thus controlling thetemperature. time and pressure under which the reactions are carriedout, it is possible to minithe product. In this treat, the temperaturein coil .29 was from 800' F. to 950 F., and the time the materialwas-resident therein was about -15 seconds. In the operation carriedoutin coil 28 the temperaturetherein was within the range of from 900 F. to1050?? and the vapors were realdent therein for about 10 seconds. In theoperation carried out in coil 29, the temperature there- Y in was withinthe range of from 925 F. to 1450' 1"., and the vapors were residenttherein for about 8 seconds.

Many modifications of my invention within the spirit thereof will occurto those skilled in this art who have read the present disclosure.

The invention claimed is: 1. A process for the production of aromatichydrocarbons from hydrocarbon oils predomiassure tained at a materiallyhigher temperature of up to-lOiiD B. than was maintained in said firstconversion zone, keeping said reaction mixture under superatmosphericpressure in said second conversion zone for a period sufllcient toobtain further formation of oleflnic hydrocarbons and cyclization ofolefinic hydrocarbons, passing the reaction mixture from said secondconversion zone into a third conversion zone maintained at a materiallyhigher temperature of up to 1450 F. than was maintained in said secondconversion zone, keeping said reaction mixture under superatmosphericpressure in said third conversion zone for a period sufiici'ent to causeconversion of the major portion of the hydrocarbons present intoaromatic hydrocarbons and withdrawing conversion products andfinely-divided catalyst from said third conversion zone.

3. A process for the production of aromatic hydrocarbons fromhydrocarbon oils predominantly non-aromatic incharacter, such askerosene or gas oil which comprises vaporizing said oil in a vaporizingzone, mixing the oil vapors with a finely-divided conversion catalystselected from the group consisting of clay, elements of the third andsixth group of the perlodic system, and

oxides of elements of the third and sixth group of the periodic system,passingthe mixture of oil vapors and finely divided catalyst undersuperatmospheric pressure through an initial conversion zone maintainedat an active conversion temperature of from about 800 F. to 975 F.,keeping said mixture within said conversion zone for a period sufilcientto obtain a substantial conversion of the initial oil into parafiinichydrocarbons of lower molecular weight and olefinic .hydrocarbons,passing the reaction mixture from said initial conversion zone to asecond conversion zone maintained at a materially higher temperature ofup to 1050 F. than was maintained in said first conversion zone, keepingsaid reaction mixture under superatmospheric pressure in said secondconversion zone for a period sufiicient to obtain further formation ofolefinic hydrocarbons the major portion of the hydrocarbons presentnantly non-aromatic in character,'such as kcrosene or gas oil whichcomprises vaporizing said oil in a vaporizing zone, mixing the oilvapors with I a finely-divided conversion catalyst selected frommaintained at an active conversion temperature.

of from about 800 F. to 975 F., keeping said mixture within saidconversion zone for a period sufflcient to obtain a substantialconversion of the initial oil into paraflinic hydrocarbons of lowermolecular weight and olefinic hydrocarbons, passin: the reaction mixturefrom said initial conversion zone to a second conversion zone mainbons.

into aromatic hydrocarbons, separating the finely divided catalyst fromthe conversion products and recovering a product rich in aromatichydrocan- 3. The process as defined in claim 2 wherein thesuperatmospheric pressure maintained in the several conversion zones isabout 40 lbs/sq. in.

4. A process for the production of aromatic hydrocarbons from a gas oilfraction having an A. P. I. gravity of 435 and boiling within the rangeof 300 lit-800 F. which comprises vaporizing said oil in a vaporizingzone, mixing the oil vapors with a finely divided conversion catalystconsisting of a mixture of chromium oxide and aluminum oxide, passingthe mixture of oil vapors and finely divided catalyst through a firstconversion zone maintained at .an active conversion, temperature of fromabout 800' I". to 975 F.,

keeping said mixture under a pressure of about 40 lbs./sq. in. in saidconversion zone for about 15 seconds to convert a substantial proportionof the initial oil into paraiiinic hydrocarbonsof lower molecular weightand oleiinic hydrocarbons, passin: the reaction mixture from saidinitial conversion zone into a second conversion zone maintained at amaterially higher temperature 01. up to about 1050 F. than wasmaintained in said first conversion zone, keeping said reaction mixtureunder a pressure of about 40 lbs/sq. in. in

said second conversion zone for about 10 seconds to eflect formation ofadditional olefinic hydrocarbons and cyclization of oleflnichydrocarbons, passins the reaction mixture from said second conversionzone into a third conversion zone maintained at a materially highertemperature of up to 1450' 1". than was maintained in said secondconversion zone. keeping said reaction mixture under a pressure of about40 1bs./sq. in. in said third reaction zone for about 8 seconds to causeconversion of the major portion of the hydrocarbons present intoaromatic hydrocarbons, withdrawing the reaction mixture from the thirdconversion zone, separating the flnaly divided catalyst from thereaction mixture and recovering from the conversion products a fractionrich in aromatic hydrocarbons.

' JESSE S. WALTON.

